CN1322218A - 无规异单烯烃/烯丙基苯乙烯共聚物和其官能化衍生物 - Google Patents
无规异单烯烃/烯丙基苯乙烯共聚物和其官能化衍生物 Download PDFInfo
- Publication number
- CN1322218A CN1322218A CN99811779A CN99811779A CN1322218A CN 1322218 A CN1322218 A CN 1322218A CN 99811779 A CN99811779 A CN 99811779A CN 99811779 A CN99811779 A CN 99811779A CN 1322218 A CN1322218 A CN 1322218A
- Authority
- CN
- China
- Prior art keywords
- multipolymer
- hydrogen
- isomonoolefin
- alkenyl
- vinylbenzene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 150000005376 secondary alkyl halides Chemical class 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 30
- -1 alkenyl vinylbenzene Chemical compound 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- NEQQUZIHFXJYLI-UHFFFAOYSA-N 1-ethenyl-4-prop-2-enylbenzene Chemical compound C=CCC1=CC=C(C=C)C=C1 NEQQUZIHFXJYLI-UHFFFAOYSA-N 0.000 claims description 13
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000011968 lewis acid catalyst Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 150000003440 styrenes Chemical class 0.000 claims description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 abstract 1
- 150000005375 primary alkyl halides Chemical class 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 54
- 238000007334 copolymerization reaction Methods 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 17
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- 125000003342 alkenyl group Chemical group 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 7
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 230000026030 halogenation Effects 0.000 description 4
- 238000005658 halogenation reaction Methods 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 229940050176 methyl chloride Drugs 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- 229920002367 Polyisobutene Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 3
- 229960001826 dimethylphthalate Drugs 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000002118 epoxides Chemical class 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 238000010550 living polymerization reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- MJMQIMYDFATMEH-UHFFFAOYSA-N 2-chloro-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)Cl MJMQIMYDFATMEH-UHFFFAOYSA-N 0.000 description 2
- KPJKMUJJFXZGAX-UHFFFAOYSA-N 2-chloropropan-2-ylbenzene Chemical compound CC(C)(Cl)C1=CC=CC=C1 KPJKMUJJFXZGAX-UHFFFAOYSA-N 0.000 description 2
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 description 2
- WYVVKGNFXHOCQV-UHFFFAOYSA-N 3-iodoprop-2-yn-1-yl butylcarbamate Chemical compound CCCCNC(=O)OCC#CI WYVVKGNFXHOCQV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001398 aluminium Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 229920005555 halobutyl Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- WOZCYBXTBXAJSA-UHFFFAOYSA-N 2-(chloromethyl)buta-1,3-diene Chemical compound ClCC(=C)C=C WOZCYBXTBXAJSA-UHFFFAOYSA-N 0.000 description 1
- AWQFNUMHFNEWGS-UHFFFAOYSA-N 2-methylprop-1-ene;styrene Chemical compound CC(C)=C.C=CC1=CC=CC=C1 AWQFNUMHFNEWGS-UHFFFAOYSA-N 0.000 description 1
- 101100029855 Arabidopsis thaliana PIP1.4 gene Proteins 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical group [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- LESMGEAJOCEPOL-UHFFFAOYSA-N C(=CCC)C=1C=C(C=C)C=CC1 Chemical compound C(=CCC)C=1C=C(C=C)C=CC1 LESMGEAJOCEPOL-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 101100010166 Mus musculus Dok3 gene Proteins 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000001743 benzylic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 229920005556 chlorobutyl Polymers 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- ASGWJZGDJGOLJJ-UHFFFAOYSA-L ethylaluminum(2+);hexane;dichloride Chemical compound [Cl-].[Cl-].CC[Al+2].CCCCCC ASGWJZGDJGOLJJ-UHFFFAOYSA-L 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 125000004968 halobutyl group Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- JUHDUIDUEUEQND-UHFFFAOYSA-N methylium Chemical compound [CH3+] JUHDUIDUEUEQND-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- QSGNIZYSOOADSE-UHFFFAOYSA-N penta-1,4-dienylbenzene Chemical compound C=CCC=CC1=CC=CC=C1 QSGNIZYSOOADSE-UHFFFAOYSA-N 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920006029 tetra-polymer Polymers 0.000 description 1
- 150000003568 thioethers Chemical group 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
本发明提供一种具有4至7个碳原子的异单烯烃并含有式(Ⅰ)表示的共聚链烯基苯乙烯部分的共聚物,其中m=0－2,n=0－20,各R1至R7独立地选自氢、C1－C10烷基和C1－C10伯或仲烷基卤化物,且R1、R2或R3中至少一个为氢,当m=1或2时,R3和R1为－CH2－。
Description
本发明背景
本发明领域
本发明涉及包括C4-C7异单烯烃和链烯基苯乙烯共聚单体的无规共聚物，及其官能化衍生物。
相关技术的描述
异丁烯与至多约4mol％的异戊二烯的卤化共聚物(丁基橡胶)是公知的聚合物材料，其硫化橡胶提供某些很多其它二烯烃基弹性体不具有的突出性能。由很多硫化的卤化弹性体制备的制品提供改进的耐油和油脂性能以及耐氧和臭氧降解的性能。丁基橡胶硫化橡胶显示优良的不渗透空气、水蒸气和很多有机溶剂的性能，以及耐老化和阳光的性能。这些性能使这些材料成为一种或多种应用如无管轮胎内衬、水管、有机流体管、轮胎结构的组分、垫圈、粘合剂组合物和各种模制品的理想候选物。
最近，一类新的卤化弹性共聚体已在例如US5,162,445中的公开文献中发现，这类材料提供很多与卤化丁基橡胶相同的性能，但具有更好的耐臭氧和溶剂性能。这些材料是C4-C7异烯烃(如异丁烯(IB))与对烷基苯乙烯共聚单体(如对甲基苯乙烯(PMS))的无规共聚物的卤化产品，其中存在于苯乙烯单体单元中的至少一些烷基取代基含有官能团，如卤素。制备的共聚物显示共聚单体均匀加入整个分子量范围内，使官能化同样均匀。PMS链段上的苄基位置可被选择性官能化为各种基团如酯、溴化物、醚、硫醚等。此外，可制备接枝共聚物。对母体共聚物官能改性导致具有令人感兴趣的和可用性能的弹性体。很多这些性能公开于’445专利、US5,430,118和US5,426,167中。卤化共聚物的最重要用途是苄基卤化物存在新的交联化学的机会，同时改进所得橡胶的氧化稳定性。该氧化稳定性是由于在共轭二烯烃的共聚产品中不存在主链双键引起的，正如丁基橡胶的情形一样。
低分子量IB/PMS共聚物是有吸引力的用于密封剂和涂料的共聚物。它们提供聚异丁烯的固有特性以及良好的耐候性，原因在于不存在链中不饱和度。此外，通用的官能化化学允许引入很多官能基团。例如，可通过两种方式引入乙烯基。金属化对甲基提供与亲电试剂如氯硅烷或烯丙基氯反应，生成乙烯基侧基。此外，IB/PMS共聚物可被卤化为苄基卤化物，然后与烯丙醇的钠盐反应生成烯丙基醚。无论何种方法，引入乙烯基侧基需要至少两个后聚合步骤。有利的是通过直接共聚合适的共聚单体制备含链烯基的IB共聚物。
乙烯基苄基氯已被用作IB共聚的共聚单体。US3,067,182公开了70至99mol％IB与30至1mol％的优选对异丙烯基苄基氯(IPBC)在惰性溶剂中，使用Friedel-Crafts催化剂在温度低于-50℃下共聚的方法。共聚乙烯基苄基氯(VBC)(间和对取代的混合物)和异丁烯的连续聚合方法公开于US4,074,035中。该方法必须将加入的VBC限制在低于5mol％，要求在共聚单体比例的精确范围内良好控制共聚单体的连续加料，以制备无凝胶的聚合物。类似的体系描述于IPBC的邻和对混合物，Jones等人，应用聚合物科学期刊(J.Appl.Polym.Sci.)，
5，452(1969)中。
烯丙基卤也已用作IB共聚中的官能单体。在US3,299,020中将甲代烯丙基氯用作共聚单体，但据说该共聚物不含烯丙基卤，因此不显示增强的硫化特性。官能团基本上丧失。由甲基烯丙基氯或2-氯甲基-1，3-丁二烯在常规阳离子聚合条件下制备氯丁基橡胶公开于Sadykh-Zade等人，Dokl.Akad.Nauk，Azerb.SSR，
24，20(1968)中。将至多2mol％的烯丙基氯引入共聚物中。在US5,342,908中将同系共聚单体用于制备卤丁基橡胶。
侧基如乙烯基链烯基和烯丙基提供另一类活性“官能”基团，这些基团可用于改性聚合物。这些基团比通过共聚共轭二烯烃形成的主链亚乙烯基和偏亚乙烯基更亲核(March，
高等有机化学(Advanced Organic Chemistry)，第4版，John Wiley & Sons，New York，1992，p748)。链烯基侧基允许活***联、接枝和化学改性。这些反应中的很多反应通过将试剂与母聚合物一起简单加热进行。此工艺不形成必须在使用前从聚合物中除去的不需要的副产品(如卤素)。由上面描述的方法制备链烯基侧基需要后聚合官能化。
直接共聚链烯基苯乙烯提供一种将该链烯基侧基引入聚异丁烯中的新方法。由这类共聚单体，迄今已制备了两种并用于阴离子聚合中：对烯丙基苯乙烯(K.C.Frisch，聚合物科学期刊(J.Polym.Sci.)，
41，359(1959)；G.F.D’Alelio，T.R.Hoffend，聚合物科学期刊，A辑-15，1245(1967)和von G.Greber，G.Egle，Makromol.Chem.
54，119(1962))和对3-丁烯基苯乙烯(von G.Greber，同上)。G.F.D′Alelio的参考文献在摘要中提及“当使用自由基和阳离子引发剂时获得交联聚合物”。此观点进一步通过第1253页上的评述和第1254页表3中的数据说明。这些参考文献教导不可能将所述单体阳离子聚合成非交联的聚合物上。未公开这些类型的共聚单体与异丁烯一起使用。
本发明概述
本发明提供一种具有4至7个碳原子的异单烯烃并含有下式I表示的共聚链烯基苯乙烯部分的共聚物：
其中m＝0-2，n＝0-20，各R1至R7独立地选自氢、C1-C10烷基和C1-C10伯或仲烷基卤化物，且R1、R2或R3中至少一个为氢，当m＝1或2时，R3和R1为-CH2-。
本发明进一步提供一种具有4至7个碳原子的异单烯烃并含有下式II表示的官能化苯乙烯类部分的官能化共聚物：
其中m、n和R1、R3-R7为上面定义的，X和Y中至少一个为含氧、硫、硅、氮、碳、卤素或磷的官能团，X和Y中不多于一个为氢。
本发明基于如下发现：含链烯基苯乙烯部分的异单烯烃共聚物可在常规碳阳离子聚合条件下制备，其中链烯基在共聚期间保持不反应，留下该基团可用于后聚合应用，例如如通过双键加成反应交联、接枝和官能化。本发明详细描述
本发明的共聚物为具有4至7个碳原子的异单烯烃与具有下式III的链烯基苯乙烯单体的直接反应产品：
其中m＝0-2，n＝0-20，各R1至R7独立地选自氢、C1-C10烷基和C1-C10伯或仲烷基卤化物，且R1、R2或R3中至少一个为氢，当m＝1或2时，R3和R1为-CH2-。优选R1-R7为C1-C10基团，m＝0，n＝0-5，更优选R1-R7为C1-C4基团，m＝0，n＝0-2，最优选n＝0，m＝0以及R1-R3、R6和R7为氢。尽管此单体的相应链烯基可处于间、邻或对位，或混合位置，但优选的位置为对位，优选的单体为4-烯丙基苯乙烯。优选的异单烯烃为异丁烯。
本发明的共聚物可在常规阳离子聚合条件下生产，由此获得具有宽数均分子量(Mn)约500至约1,000,000.00、平均分子量分布Mw/Mn(重均分子量除以数均分子量)低于约6，优选低于约4，更优选低于约2.5的共聚物产品。所有分子量测定都通过凝胶渗透色谱(GPC)进行。这些共聚物还具有基本上均匀的组成分布特征，即它们为在所有选取的共聚物部分具有基本上相同的异单烯烃与链烯基苯乙烯共聚单体比例的无规共聚物。
这些共聚物可含有约0.1至99.9mol％的链烯基苯乙烯部分和约99.9mol％至0.1mol％的异单烯烃。含较大量链烯基苯乙烯部分(即大于50mol％)的共聚物趋于为热塑性和树脂特性的，而含较高量的异单烯烃的共聚物趋于为弹性和橡胶特性的。优选的共聚物为含约0.5至20mol％，更优选0.75至约10mol％链烯基苯乙烯部分和相应99.5至80mol％，或99.25至90mol％异单烯烃的弹性共聚物。用于共聚的一部分链烯基苯乙烯单体可被一种或多种其它阳离子可聚合单体，如其它苯乙烯类单体例如苯乙烯、对甲基苯乙烯和α-甲基苯乙烯，共轭α-二烯烃如异戊二烯，丁二烯和环戊二烯，以及类似单体替代以生产三元共聚物或四元共聚物。
本发明的异丁烯和链烯基苯乙烯共聚单体容易在阳离子条件下聚合。聚合可借助路易斯酸催化进行。传统的和活性聚合***都是可行的。用于该方法的合适路易斯酸催化剂应比三氯化铝弱。优选的催化剂为基于元素周期表第4、5、13、15和15族的金属如硼、铝、镓、铟、钛、锆、锡、钒、砷、锑和铋的路易斯酸。较弱的路易斯酸的非限制性例子包括二氯化乙基铝、二溴化乙基铝、二氯化甲基铝、二溴化甲基铝、氯化二乙基铝、溴化二乙基铝、溴化二甲基铝、氯化二甲基铝、烷基铝氧烷如甲基铝氧烷，三氯化硼、三溴化硼、三(五氟苯基)硼、四氯化钛、四溴化钛、四氯化钒和四溴化钒。
优选的路易斯酸催化剂可与引发剂如叔烷基或芳烷基卤化物、醚或酯并用。优选的非限制性例子包括2-氯-2-甲基丙烷、2-氯-2，4，4-三甲基戊烷、1，3，5-三(1-氯-1-甲基乙基)苯和5-叔丁基-1，3-二(1-氯-1-甲基乙基)苯。其它合适的引发剂可在US4,946,899中找到。
已发现上述较弱路易斯酸中几种可用于活性异丁烯聚合中。异丁烯活性聚合可使用各种方法实现，其中一些方法描述于US5,506,316、5,418,303、5,350,819、5,169,914和4,910,321中。这些***还适合本发明的异丁烯与链烯基苯乙烯共聚单体共聚。
可实现活性聚合的一般性条件包括：
(1)一种催化剂，包括引发剂叔烷基卤化物、叔芳烷基卤化物、叔烷基醚、叔芳烷基醚、叔烷基酯、叔芳烷基酯等；
(2)一种路易斯助引发剂，通常包括钛、硼或铝的卤化物；
(3)一种质子清除剂和/或电子给体；
(4)一种溶剂，其介电常数按照已知的阳离子聚合***基于选择的路易斯酸和单体选取；和
(5)单体。
使用的催化剂量取决于生产的共聚物所需的分子量和所需的分子量分布。该范围通常为约1×10-5mol/L至2×10-2mol/L，最优选10-4至10-1mol/L。
用于单体、催化剂组分和聚合反应产品的合适稀释剂包括单独或作为混合物使用的常规脂族和芳族烃类，和以与烃稀释剂的混合物形式使用的C1至C6卤代烃(其用量为加入反应区的总稀释剂体积的至多约100％)。通常当单体溶于选取的稀释剂中时，催化剂可不必溶于其中。优选的稀释剂包括烃如己烷、戊烷、异丁烷等；烷基卤化物如氯甲烷、二氯甲烷等，芳族卤化物如氯苯，二硫化碳、二氧化碳和其混合物。这些方法中的一种典型方法描述于US5,543,479中，该专利公开的内容这里作为参考引入。
聚合可在任何合适的常规容器或反应器(如用于制造丁基橡胶或异丁烯/对甲基苯乙烯共聚物中的那些)中进行。该反应在温度低于0℃，优选-10℃至约-155℃下进行，反应时间应足以生产所需分子量的共聚物，例如从低于1分钟至5小时，更优选约5至60分钟。该聚合反应可通过加入猝灭剂如低级烷基醇终止，接着回收并洗涤聚合物产品。用于制备本发明共聚物的合适反应器和反应条件更特别描述于US5,162,445中，该专利公开的内容这里作为参考引入。
本发明具有平均Mn低于约20,000的共聚物特别适合用于密封剂和涂料应用中，而具有Mn高于100,000的那些特别适用于诸如轮胎内衬、水管、有机流体管、垫圈、粘合剂组合物、驱动皮带和各种模制品应用中。这些共聚物容易用常规的含硫硫化配方、过氧化物硫化配方和其它用于硫化饱和或不饱和弹性聚合物的硫化体系交联(硫化)。接枝共聚物可通过使用常规自由基聚合方法在含链烯基侧基的预形成异单烯烃/链烯基苯乙烯共聚物存在下聚合一种自由基可聚合单体或其混合物制备。
本发明还涉及上述式II的结构的官能化共聚物，其中m＝0-2，n＝0-20，R1和R3独立地选自氢、C1-C10烷基和C1-C10伯或仲烷基卤化物，X和Y中至少一个为含氧、硫、硅、氮、碳、卤素或磷中至少一种元素的官能团，X和Y中不多于一个为氢。
上述II中描述的共聚物的官能化变型可通过常规公知的化学反应，如通过将选取的反应试剂与链烯基苯乙烯聚合物简单加热，或通过加成反应如环氧化、卤化、Diels-Alder环化和涉及链烯基侧基部分的类似反应制备。用于获得一些代表性的不同官能化共聚物的典型的具体官能基、一般反应类型和典型试剂在表A中列出。
表A P＝聚合物
实施例
为说明本发明，提供如下实施例。这些实施例并不意味着在任何方面限制本发明，而是仅用于说明本发明。分子量值(Mw和Mn)通过使用装有DRI(差示折射率)检测器和设定至254nm的UV检测器的Waters 150C凝胶渗透色谱仪由凝胶渗透色谱测量。用窄分子量的聚异丁烯标准物绘制校准曲线。用市购的标准凝胶渗透软件包进行数据分析。在250MHz Bruker AC-250光谱仪上由质子NMR自CDCl3溶液测定百分共聚单体加入量、百分BSB(异丁烯-苯乙烯类单体-异丁烯三单元组)和百分双键保持率。
实施例1-8
实施例1-8的共聚物通过将3ml异丁烯与按表1中给出的浓度的4AS(4-烯丙基苯乙烯)和TMPCl(2-氯-2，4，4-三甲基戊烷)一起溶于12ml无水己烷和8ml氯甲烷中在-80℃下制备。共聚通过加入催化剂(EADC：二氯化乙基铝、DMAC：氯化二甲基铝)起始并连续进行15分钟。通过加入冷冻的甲醇使聚合停止。通过在甲醇中沉淀分离共聚物并真空干燥。共聚结果也在表1中列出。对于各制备的共聚物DRI和UV结果可叠加。1H-NMR证实烯丙基双键100％保留。
实施例9和10
这些共聚物按与实施例1-8类似的方式制备。在实施例9中，将3ml异丁烯与4AS和TMPCL一起溶于20ml己烷中。在实施例10中，将10ml异丁烯与4AS和叔丁基氯一起溶于66ml己烷中。按表1中给出的浓度加入4AS和TMPCL。按前述方法分离共聚物。所得结果也在表1中列出。对于各制备的共聚物DRI和UV结果可叠加。1H-NMR证实烯丙基双键100％保留。
实施例11-13
对于实施例11-13，共聚物通过将40ml己烷、26ml氯甲烷、邻苯二甲酸二甲酯和0.85ml的2.5mol/L DMAC己烷溶液加入小型树脂釜中在-80℃下制备。将该溶液熟化3分钟，然后加入10ml异丁烯(在实施例13中为18ml)。然后将该溶液再熟化3分钟。将4AS和TMPCL分别溶于1ml己烷中(在实施例13中为12ml己烷和1.3ml氯甲烷)。聚合通过加入最后这种溶液(冷冻至-80℃)起始。50分钟后(在实施例13中为46分钟)停止共聚，并按实施例1-8中所述精制。4AS、TMPCL和邻苯二甲酸二甲酯的浓度及共聚结果在表2中给出。对于各制备的共聚物DRI和UV结果可叠加。1H-NMR证实烯丙基双键100％保留。
实施例14
共聚物通过将37ml己烷、7ml异丁烯、1.3ml 4AS和5.6微升TMPCL在树脂釜中混合而于-30℃下制备。聚合通过加入25微升2.5mol/L EADC己烷溶液起始。在26分钟后通过加入冷冻的甲醇使聚合停止。回收5.1g(87％)共聚物。该共聚物具有Mn2470和Mw/Mn5.8。GPC的UV和DRI结果可叠加。该共聚物含7.7mol％4AS和20％BSB，烯丙基双键100％保留。
实施例15
共聚物通过将37ml己烷、10微升TMPC L、1.7ml 4AS和9ml异丁烯在树脂釜中混合而于-30℃下制备。聚合通过加入38微升2.5mol/L二氯化乙基铝己烷溶液起始。在15分钟后通过加入冷冻的甲醇使聚合停止。回收的6.4g(85％)共聚物具有Mn2840和Mw/Mn6.9。GPC的UV和DRI结果可叠加。该共聚物含8.0mol％4AS和32％BSB，烯丙基双键100％保留。
实施例16和17
这些共聚物通过将53ml己烷、13ml氯甲烷、13微升TMPCL、3BS(4-(3′-丁烯基)苯乙烯)和异丁烯混合在-80℃下制备。共聚通过加入40微升2.5mol/L EADC己烷溶液起始。共聚进行45分钟，然后按上述方法停止。异丁烯和3BS的浓度以及聚合结果在表3中列出。对于各制备的共聚物UV和DRI结果可叠加。1H-NMR证实乙烯基双键100％保留。
实施例18-22
这些共聚物在-80℃下通过将40ml己烷、28ml氯甲烷和1.4ml2.5mol/L DMAC己烷溶液混合并将该溶液熟化制备。3分钟后，加入18ml异丁烯。将该溶液再熟化3分钟。分别制备3BS在2ml己烷和1.3ml氯甲烷中的溶液。在第二个三分钟结束后，立即加入3BS溶液，接着加入13.8微升TMPCL。共聚连续进行60分钟，然后按前述方法猝灭和精制。表3给出IB和3BS的浓度以及共聚结果。对于各制备的共聚物UV和DRI结果可叠加。1H-NMR证实双键100％保留。
实施例23-28
这些共聚在-30℃下进行。将37ml己烷与9ml异丁烯、10微升TMPCL和3BS混合。共聚通过加入2.5mol/L EADC(二氯化乙基铝)己烷溶液起始。共聚进行15分钟，然后按上述方法猝灭和精制。3BS和EADC的浓度以及聚合结果在表4中列出。对于各制备的共聚物UV和DRI结果可叠加。1H-NMR证实双键100％保留。官能基团转化实施例
实施例29
将0.5g实施例11的共聚物溶于50ml氯仿中。单独将226mgMCPBA(间氯过氧苯甲酸)溶于/悬浮于5ml氯仿中。将这两种溶液混合并将其在室温下搅拌过夜。然后将聚合物在甲醇中沉淀，接着真空干燥。将干燥的聚合物用1H-NMR表征，发现84％的烯丙基转化为环氧化物。实施例30
本实施例中，将0.366g实施例14的共聚物与418mg MCPBA一起使用。反应按与实施例29相同的方式进行。将干燥的聚合物用1H-NMR表征，发现100％的烯丙基转化为环氧化物。
实施例31
将0.5g实施例17的共聚物与200mg MCPBA一起在类似于实施例29的条件下使用。将干燥的聚合物用1H-NMR表征，发现10％的烯丙基转化为环氧化物。
实施例32
将0.37g实施例14的共聚物在氮气下溶于无水18ml四氢呋喃中。在该溶液中注射入2.3ml 0.5mol/L 9-硼杂双环[3.3.1]壬烷。将该反应进行3天。通过滴加入15ml 2.5mol/L磷酸二氢钠和磷酸氢钾溶液及0.37ml 30％过氧化氢水溶液使硼烷还原。将该反应进行1小时。然后分离出有机相并倒入丙酮中。将聚合物溶于80份甲苯和20份异丙醇的溶液中，并在甲醇中再沉淀。将聚合物真空干燥。聚合物的1H-NMR表征显示100％的烯丙基双键转化为伯醇。
实施例33
将0.5g实施例25的共聚物溶于10ml氯苯中，并在氢化钙上干燥2小时。然后将该溶液过滤除去氢化钙。然后加入70微升二甲基苯基硅烷和0.16g六氯铂酸。将反应物料加热并在80℃下搅拌2小时。冷却后，将溶液过滤并在真空下除去氯苯。将该聚合物再溶于氯仿中，然后用水洗涤，并用活性炭处理以除去颜色。将该溶液过滤并在真空下除去溶剂。产品的1H-NMR显示双键完全转化为有机硅烷。表1
表2
表3
表4
| 实施例 | [引发剂](mol/L) | 催化剂，[催化剂](mol/L) | [4-AS](mol/L) | 时间(分钟) | 产量(g) | Mn | Mw/Mn | 共聚单体结合％ | ％BSB |
| 1 | 8.3×10-4 | EADC，1.7×10-3 | 3.3×10-2 | 15 | 2.1 | 8,390 | 5.3 | 1.4 | 70 |
| 2 | 6.2×10-4 | DMAC，2.8×10-2 | 3.3×10-2 | 30 | 2.2 | 146,500 | 1.7 | 2.0 | 54 |
| 3 | 6.2×10-4 | DMAC，2.8×10-2 | 3.3×10-2 | 30 | 2.2 | 125,400 | 1.7 | 1.3 | 61 |
| 4 | 6.2×10-4 | DMAC，2.8×10-2 | 6.6×10-2 | 30 | 2.2 | 114,400 | 1.7 | 2.6 | 50 |
| 5 | 6.2×10-4 | DMAC，2.8×10-2 | 9.9×10-2 | 30 | 2.2 | 132,700 | 1.5 | 3.9 | 34 |
| 6 | 6.2×10-4 | EADC，1.7×10-3 | 3.3×10-2 | 15 | 2.2 | 20,100 | 4.4 | 1.2 | 71 |
| 7 | 6.2×10-4 | EADC，1.7×10-3 | 6.6×10-2 | 15 | 2.2 | 18,000 | 4.4 | 2.3 | 60 |
| 8 | 6.2×10-4 | EADC，1.7×10-3 | 9.9×10-2 | 15 | 2.2 | 21,200 | 3.9 | 3.7 | 49 |
| 9 | 6.2×10-4 | EADC，1.7×10-3 | 3.0×10-2 | 15 | 2.1 | 41,300 | 3.8 | 1.0 | 80 |
| 10 | 8.6×10-4 | EADC，8.8×10-4 | 2.9×10-2 | 60 | 3.8 | 116,700 | 3.2 | 4.0 | 42 |
| 实施例 | [引发剂](mol/L) | [邻苯二甲酸二甲酯](mol/L) | [4-AS](mol/L) | 产量(g) | Mn | Mw/Mn | 共聚单体结合％ | ％BSB |
| 11 | 6.2×10-4 | 8.0×10-5 | 2.9×10-2 | 5.7 | 130,000 | 1.2 | 1.2 | 64 |
| 12 | 6.2×10-4 | 8.0×10-5 | 7.3×10-2 | 7.4 | 121,700 | 1.5 | 3.6 | 36 |
| 13 | 7.6×10-4 | 1.5×10-4 | 4.9×10-2 | 12.0 | 157,100 | 1.16 | 1.3 | 59 |
| 实施例 | [1B](mol/L) | [3BS](mol/L) | 产量(g) | Mn | Mw/Mn | 共聚单体结合％ | ％BSB |
| 16 | 1.6 | 7.4×10-2 | 6.6 | 8,080 | 5.6 | 3.4 | 44 |
| 17 | 1.5 | 3.8×10-2 | 5.6 | 9,020 | 6.1 | 2.0 | 20 |
| 18 | 2.5 | 4.8×10-2 | 11.8 | 112,100 | 1.8 | 1.2 | 66 |
| 19 | 2.5 | 9.0×10-2 | 12.5 | 174,000 | 2.0 | 2.6 | 46 |
| 20 | 2.5 | 4.5×10-2 | 11.6 | 90,700 | 2.0 | 1.5 | 62 |
| 21 | 2.5 | 9.0×10-2 | 11.8 | 141,200 | 1.7 | 2.9 | 48 |
| 22 | 2.5 | 1.4×10-1 | 13.0 | 85,600 | 2.1 | 4.0 | 37 |
| 实施例 | [3BS](mol/L) | [EADC](mol/L) | 产量(g) | Mn | Mw/Mn | 共聚单体结合％ | ％BSB |
| 23 | 0.21 | 1.2×10-2 | 6.3 | 14,200 | 3.3 | 14.2 | 8 |
| 24 | 0.11 | 2.1×10-3 | 6.0 | 6,480 | 4.1 | 4.7 | 26 |
| 25 | 0.11 | 2.0×10-3 | 5.9 | 5,420 | 2.8 | 4.6 | 37 |
| 26 | 0.11 | 1.2×10-2 | 5.9 | 4,300 | 3.3 | 4.1 | 38 |
| 27 | 0.22 | 1.2×10-2 | 6.9 | 3,480 | 3.7 | 7.5 | 20 |
| 28 | 0.33 | 1.2×10-2 | 7.8 | 6,180 | 4.1 | 9.3 | 10 |
Claims (8)
1.一种具有4至7个碳原子的异单烯烃并含有下式表示的链烯基苯乙烯部分的共聚物：其中m＝0-2，n＝0-20，各R1至R7独立地选自氢、C1-C10烷基和C1-C10伯或仲烷基卤化物，且R1、R2或R3中至少一个为氢，当m＝l或2时，R3和R1为-CH2-。
2.权利要求1的共聚物，含0.1至99mol％的所述链烯基苯乙烯和99.9至1mol％的所述异单烯烃。
3.权利要求1的共聚物，其中所述链烯基苯乙烯由下式表示：
其中各R1、R2、R3、R6和R7独立地选自氢、C1-C10烷基和C1-C10伯或仲烷基卤化物，且R1、R2或R3中至少一个为氢。
4.权利要求1的共聚物，其中R6和R7各自为氢。
5.权利要求2的共聚物，含约0.5至20mol％的所述链烯基苯乙烯和约99.5至80mol％的所述异单烯烃。
6.权利要求1的共聚物，其中所述异单烯烃为异丁烯，和所述链烯基苯乙烯为4-烯丙基苯乙烯。
7.一种具有4至7个碳原子的异单烯烃并含有下式表示的官能化苯乙烯类部分的官能化共聚物：
其中m＝0-2，n＝0-20，各R1至R7独立地选自氢、C1-C10烷基和C1-C10伯或仲烷基卤化物，且R1、R2或R3中至少一个为氢，当m＝1或2时，R3和R1为-CH2-，X和Y中至少一个为含氧、硫、硅、氮、碳、卤素或磷的官能团，X和Y中不多于一个为氢。
8.一种制备具有4至7个碳原子的异烯烃并含有下式表示的链烯基苯乙烯部分的共聚物的方法：其中m＝0-2，n＝0-20，各R1至R7独立地选自氢、C1-C10烷基和C1-C10伯或仲烷基卤化物，且R1、R2或R3中至少一个为氢，当m＝1或2时，R3和R1为-CH2-，
所述方法包括将异烯烃和苯乙烯类部分在包括路易斯酸催化剂的阳离子聚合条件下接触，所述路易斯酸催化剂比三氯化铝弱。
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| Application Number | Priority Date | Filing Date | Title |
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| US09/167,787 US6274689B1 (en) | 1998-10-07 | 1998-10-07 | Random isomonoolefin/allyl styrene copolymers and functionalized derivatives thereof |
| US09/167,787 | 1998-10-07 |
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| US (1) | US6274689B1 (zh) |
| EP (1) | EP1123326A1 (zh) |
| JP (1) | JP2002526612A (zh) |
| KR (1) | KR20010075583A (zh) |
| CN (1) | CN1322218A (zh) |
| BR (1) | BR9914350A (zh) |
| CA (1) | CA2340773A1 (zh) |
| CZ (1) | CZ20011238A3 (zh) |
| HU (1) | HUP0103808A3 (zh) |
| PL (1) | PL346239A1 (zh) |
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| WO (1) | WO2000020474A1 (zh) |
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| US6858690B2 (en) * | 1999-11-15 | 2005-02-22 | Exxonmobil Chemical Patents Inc. | Process for polymerizing cationically polymerizable monomers |
| CA2390046A1 (en) * | 2002-06-28 | 2003-12-28 | Bayer Inc. | Method for improving the processability of butyl polymers |
| US7991730B2 (en) * | 2007-07-17 | 2011-08-02 | Novalyst Discovery | Methods for similarity searching of chemical reactions |
| JP2010090273A (ja) * | 2008-10-08 | 2010-04-22 | Nagoya Univ | β−ピネン重合体の製造方法 |
| ES2973829T3 (es) * | 2017-10-14 | 2024-06-24 | Tpc Group Llc | Copolímeros de isobutileno no aleatorios |
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| US2830973A (en) * | 1955-12-09 | 1958-04-15 | Exxon Research Engineering Co | Preparation of olefin-aromatic copolymers with cross-linking agents |
| US2989515A (en) * | 1956-08-13 | 1961-06-20 | Du Pont | Process of copolymerizing aromatic dienes and monoolefins with catalyst of metal halide and organometal compound |
| US3067182A (en) | 1959-08-03 | 1962-12-04 | Dow Chemical Co | Isopropenylbenzyl chloride and polymers thereof |
| US3299020A (en) | 1963-12-24 | 1967-01-17 | Exxon Research Engineering Co | Olefin-allyl halide copolymer |
| JPS50136315A (zh) | 1974-04-17 | 1975-10-29 | ||
| US4074035A (en) | 1975-04-22 | 1978-02-14 | Exxon Research & Engineering Co. | Halomethylated aromatic interpolymers |
| US4910321A (en) | 1985-06-20 | 1990-03-20 | University Of Akron | Living catalysts, complexes and polymers therefrom |
| IT1196987B (it) | 1986-07-23 | 1988-11-25 | Enichem Sintesi | Copolimeri sililati dell'isobutilene reticolabili in condizioni ambientali e procedimento per la loro preparazione |
| JPH0672173B2 (ja) | 1987-02-20 | 1994-09-14 | 日本ペイント株式会社 | グラフト重合体およびその製造方法 |
| DE3803545A1 (de) * | 1987-06-19 | 1988-12-29 | Orpegen Med Molekularbioforsch | Allylische seitenketten enthaltendes festphasensystem, verfahren zu seiner herstellung und seine verwendung in festphasenreaktionen |
| US5430118A (en) | 1988-05-27 | 1995-07-04 | Exxon Chemical Patents Inc. | Para-alkylstyrene/isoolefin copolymers having substantially homogeneous compositional distribution |
| US5162445A (en) | 1988-05-27 | 1992-11-10 | Exxon Chemical Patents Inc. | Para-alkylstyrene/isoolefin copolymers and functionalized copolymers thereof |
| US5169914A (en) | 1988-05-03 | 1992-12-08 | Edison Polymer Innovation Corporation | Uniform molecular weight polymers |
| WO1992011295A1 (en) | 1990-12-20 | 1992-07-09 | Exxon Chemical Patents Inc. | Uv/eb curable butyl copolymers for coating applications |
| JP3154529B2 (ja) | 1991-10-14 | 2001-04-09 | 鐘淵化学工業株式会社 | 官能基を有するイソブチレン系重合体及びその製造法 |
| US5342908A (en) | 1993-02-05 | 1994-08-30 | Polysar Rubber Corporation | Process for preparing halobutyl-type polymer |
| US5506316A (en) | 1993-02-19 | 1996-04-09 | Exxon Chemical Patents Inc. | Carbocationic catalysts and process for using said catalysts |
| US5350819A (en) | 1993-02-19 | 1994-09-27 | Exxon Chemical Patents Inc. | Carbocationic catalysts and process for using said catalysts |
| US5350726A (en) | 1993-09-03 | 1994-09-27 | Exxon Chemical Patents Inc. | Carbocationic catalysts and process for using said catalysts |
| WO1995007945A1 (en) | 1993-09-17 | 1995-03-23 | Exxon Research & Engineering Company | Novel functionalized isoolefin/para-alkylstyrene copolymers |
| DE4428024A1 (de) | 1994-08-08 | 1996-02-15 | Bayer Ag | Verfahren zur Herstellung von Polyisoolefinen |
| DE19628450A1 (de) | 1996-07-15 | 1998-01-22 | Bayer Ag | Verfahren zur Herstellung von hochverzweigten Polyisoolefinen |
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| CA2340773A1 (en) | 2000-04-13 |
| BR9914350A (pt) | 2001-06-26 |
| WO2000020474A1 (en) | 2000-04-13 |
| TW500732B (en) | 2002-09-01 |
| JP2002526612A (ja) | 2002-08-20 |
| HUP0103808A2 (hu) | 2002-02-28 |
| HUP0103808A3 (en) | 2003-02-28 |
| KR20010075583A (ko) | 2001-08-09 |
| US6274689B1 (en) | 2001-08-14 |
| PL346239A1 (en) | 2002-01-28 |
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